Fungicidal methods, compounds and compositions containing benzophenones

ABSTRACT

There is provided a method for the control of phytopathogenic fungi and disease caused thereby which comprises contacting said fungi with a fungicidally effective amount of a benzophenone compound of formula I ##STR1## There are further provided benzophenone compounds of formula Ia which are useful as fungicidal agents and compositions useful for the protection of plants from the damaging effects of phytopathogenic fungi and fungal disease.

BACKGROUND OF THE INVENTION

Food production relies upon a variety of agricultural technologies toensure the growing population's dietary needs remain affordable,nutritious and readily available on grocery store shelves. Fungicidesare one of these agricultural technologies which are available to theworld community. Fungicides are agrochemical compounds which shieldcrops and foods from fungus and fungal diseases. Crops and food areconstantly threatened by a variety of fungal organisms, which, if leftuncontrolled, can cause ruined crops and devastated harvests.

In particular, ascomycetes, the causative agent for powdery mildewdiseases are an ever-present threat especially to cereal and fruitcrops. However, applications of fungicidal agents at disease controlrates can cause phytotoxic damage to the target plants.

Therefore it is an object of this invention to provide a method tocontrol phytopathogenic fungus without causing concurrent phytotoxicdamage to the host plant.

It is another object of this invention to provide an effective and safemethod for the protection of important agronomic crops from the damageand loss caused by a phytopathogenic fungal infection and the diseasecaused thereby.

It is a further object of this invention to provide benzophenonefungicidal agents and fungicidal compositions comprising a benzophenonecompound.

These and other objects and features of the invention will becomeapparent from the detailed description provided hereinbelow.

SUMMARY OF THE INVENTION

The present invention provides a method for the control of aphytopathogenic fungus or a disease caused thereby which comprisescontacting said fungus with a fungicidally effective amount of abenzophenone compound of formula I ##STR2## wherein R¹ represents ahalogen atom, an optionally substituted alkyl or alkoxy group, a cyanoor a nitro group; m is 0 or an integer of 1, 2, 3 or 4; R² independentlyrepresents a halogen atom, an optionally substituted alkyl or alkoxygroup, a nitro group or when R¹ and R² are attached to adjacent carbonatoms, R¹ and one R² may be taken together to represent --CH═CH--CH═CH--or optionally substituted alkylene or oxyalkyleneoxy; R³ representshydrogen, halogen, an optionally substituted alkyl, alkoxy, alkenyl,alkylthio, alkylsulphinyl, alkylsulphonyl, cyano, carboxy, hydroxy,nitro, or an optionally substituted amino group; R⁴ represents ahydrogen atom or an optionally substituted alkyl or acyl group; R⁵represents a hydrogen, halogen, an optionally substituted alkyl, alkoxy,alkenyloxy, alkynyloxy, alkylthio, cycloalkyl, cycloalkyloxy, hydroxy,trialkylsilyloxy group, --ONa, --OK, --OC(O)R⁷, --OCHR⁸ C(O)R⁷,--OC(O)NR⁸ R⁹, --OS(O)₂ R⁸, --OS(O)₂ NR⁸ R⁹, --OP (X¹)(OR⁸)OR⁹,--OP(X¹)(R⁸)R⁹, --S(O)R⁸, --S(O)₂ R⁸, or R⁴ and R⁵ may be taken togetherto represent an optionally substituted alkylene or alkyleneoxy chain; nis 0, or an integer of 1 or 2; R⁶ independently represents a halogenatom, an optionally substituted alkyl, alkenyl, alkynyl, alkoxy,alkenyloxy, alkynyloxy, cycloalkyl, cycloalkoxy, hydroxy, --OC(O)R¹⁰group, or when R5 and R6 are attached to adjacent carbon atoms, R⁵ andone R⁶ may be taken together to represent --CH═CH--CH═CH-- or anoptionally substituted oxyalkyleneoxy chain; R⁷ represents a hydrogenatom or an optionally substituted alkyl or alkoxy group; R⁸, R⁹ and R¹⁰independently represent a hydrogen atom, an alkyl group, or R⁸ and R⁹may be taken together to represent an alkylene chain optionallyinterrupted by an oxygen or nitrogen atom; X represents an oxygen atom,a sulphur atom or a group NOR; X¹ represents an oxygen or sulphur atom;Y represents an oxygen or sulphur atom or a sulphonyl or sulphinylgroup; and R represents a hydrogen atom or an optionally substitutedalkyl, aralkyl, aryl or acyl group.

The present invention also provides crop protection methods, fungicidalbenzophenone compounds of formula Ia, methods of preparation of saidbenzophenone compounds and fungicidal compositions comprising at leastone formula I or Ia compound and an agriculturally acceptable carrier.

DETAILED DESCRIPTION OF THE INVENTION

Huge economic losses have resulted from the devastation and damage ofimportant agronomic and horticultural crops caused by fungal infectionand infestation. Pest management strategies, field resistance, andvirulent strains have all contributed to agriculturalists' concerns forcombatting phytopathogenic fungal disease. In particular, ascomycetes,the causative agents for powdery mildew diseases continues to be aserious concern in cereal crop and fruit production. Further, in avariety of fungicidal agent applications concomitant phytotoxic injuryto the host plant may be observed.

It has now been found that benzophenone compounds of formula I arehighly effective fungicidal agents and are particularly effective forcontrolling mildew diseases such as powdery mildew. Compounds of formulaI useful in fungus control methods are those benzophenones having thestructure ##STR3## wherein X, Y, R¹, R², R³, R⁴, R⁵, R⁶, m and n aredescribed hereinabove.

Alkyl as a substituent or as a part of other substituents, such asalkoxy or alkylthio may be straight-chain or branched and may contain upto eighteen, preferably up to 14, and especially up to 10, carbon atoms,individual examples including: methyl, ethyl, propyl, butyl, pentyl,hexyl, etc. as well as their isomers such as isopropyl, isobutyl,tertiary-butyl, isopentyl, and the like. Lower alkyl or alkoxy groupshave from 1 to 10 carbon atoms. A cycloalkyl moiety as a substituent oras a part of other substituents suitably contains from 3 to 10,preferably from 3 to 6, carbon atoms. An alkenyl or alkynyl groupsuitably has from 2 to 6, preferably from 2 to 4 chain members, forexample, ethenyl, propenyl, allyl, butenyl and the like as well as forchains with more than one double bond such as pentadienyl and the like.An alkylene chain usefully has 1 to 5, preferably 1 to 4, members.

An acyl group is formally formed by the removal of hydroxyl from acarboxyl group, and is used herein to include formyl and optionallysubstituted alkylcarbonyl and arylcarbonyl groups.

A halogen atom represents fluorine, chlorine, bromine and iodine,preferably chlorine. Preferred haloalkyl moieties are difluoromethyl andtrifluoromethyl.

Optionally substituted moieties may be unsubstituted or have from one upto the maximal chemically possible number of substituents. Optionalsubstituents may be any of those customarily employed in the developmentof biocidal compounds, and/or the modification of such compounds toinfluence their activity, persistence, penetration and any otherproperty. Specific examples of such substituents include halogen,especially fluorine, chlorine or bromine, phenyl, alkylphenyl,alkoxyphenyl, halophenyl, phenyloxy, nitro, cyano, acyl, hydroxy, alkyl,alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkoxy, carboxyl, amino,alkylamino, dialkylamino, cycloalkylamino, piperidyl, morpholinyl,carbamoyl, mono- or dialkylcarbamoyl, morpholinocarbonyl, trialkylsilyland the like. Alkyl moieties of such optional substituents usefully havefrom 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms.

The benzophenone compounds according to formula I are oils, gums, or,predominantly, crystalline solid materials and possess valuablefungicidal properties. For example, they can be used in agriculture, orrelated fields such as horticulture and viticulture, for the control ofphytopathogenic fungi, especially ascomycetes, and powdery mildewdisease such as Erysiphe graminis, Podosphaera leucotricha, Uncinulanecator and the like. Said benzophenone compounds possess a highfungicidal activity within a wide concentration range and may be used inagriculture without harmful phytotoxic effects.

Preferred formula I compounds useful in the method of invention arethose in which R¹ represents a halogen atom or an optionally substitutedalkyl or alkoxy group; m is 0 or an integer of 1, 2 or 3; and R²independently represents a halogen atom or an optionally substitutedalkyl or alkoxy group; or R¹ R² together represent --CH═CH--CH═CH-- oralkylene; R³ represents a halogen atom, an optionally substituted alkyl,alkenyl, alkylthio or alkylsulphonyl group, a nitro group, or anoptionally substituted amino group; R⁵ represents a hydrogen atom, anoptionally substituted alkyl, alkoxy, alkenyloxy, alkynyloxy,cycloalkoxy or alkylthio group, a hydroxy group, a trialkylsilyloxygroup, or a --OC(O)R⁷, --OCHR⁸ C(O)R⁷, --OC(O)NR⁸ R⁹, --OS(O)₂ ^(R) ⁸ or--OS(O)₂ NR⁸ R⁹ group; or R⁴ and R⁵ together represent an optionallysubstituted alkyleneoxy chain; n is 0 or the integer 1; R⁶ represents anoptionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy,alkynyloxy, cycloalkyl or cycloalkoxy group or a --OC(O)R¹⁰ group; R⁷represents a hydrogen atom or an alkyl or alkoxy group; X represents anoxygen atom or an NOR group; and R represents a hydrogen atom or anoptionally substituted alkyl group.

Good control of phytopathogenic fungi is obtained with a fungicidallyeffective amount of a compound of formula I wherein R¹ represents ahalogen atom or an optionally substituted lower alkyl group; m is aninteger of 1 or 3; R² independently represents a halogen atom or anoptionally substituted lower alkyl group; R³ represents a halogen atom,an optionally substituted alkyl or alkenyl group, or an optionallysubstituted amino group; R⁵ represents an optionally substituted alkyl,alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy or alkylthio group or R⁴ andR⁵ may be taken together to represent an optionally substitutedalkyleneoxy chain; n is 0 or the integer 1; R⁶ represents an optionallysubstituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy,cycloalkyl or cycloalkoxy group or a --OC(O)R¹⁰ group; R⁷ represents analkyl or alkoxy group; X represents an oxygen atom or NOR group; Yrepresents an oxygen atom; and R represents hydrogen or C₁ -C₄ alkyl.

Especially preferred are those formula I compounds in which R¹represents a halogen atom or C₁ -C₄ alkyl group; R² independentlyrepresents a halogen atom or C₁ -C₄ alkyl group; R³ represents a halogenatom or an optionally substituted C₁ -C₄ alkyl group; R⁴ represents anoptionally substituted C₁ -C₄ alkyl group; R⁵ represents an optionallysubstituted lower alkyl, alkoxy, alkenyloxy, alkynyloxy or cycloalkoxygroup; R⁶ represents an optionally substituted C₁ -C₆ alkoxy,alkenyloxy, alkynyloxy or cyloalkoxy group

Effective control of phytopathogenic fungi may be achieved, for example,with a fungicidally effective amount of one or more of the followingcompounds:

2,3,5,6-tetramethyl-4',5',6'-trimethoxy-2'-methylbenzophenone;

2,6-dichloro-4',5'-dimethoxy-2'-methylbenzophenone-O-methyloxime;

2,6-dichloro-5'-t-butoxy-4'-methoxy-2'-methylbenzophenone;

2,6-dichloro-5',6'-di-n-butoxy-4'-methoxy-2'-methylbenzophenone;

2'-allyloxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone;

2'-benzyloxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone;

2'-butoxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone;

2'-cyclohexylmethoxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone;

2'-cyclopentyloxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone;

2,6-dichloro-2',3',4'-trimethoxy-6'-methylbenzophenone;

2,6-dichloro-2'-ethoxy-3',4'-dimethoxy-6'-methylbenzophenone;

2,6-dichloro-2-heptyloxy-3',4'-dimethoxy-6'-methylbenzophenone;

2,6-dichloro-2-hexyloxy-3',4'-dimethoxy-6'-methylbenzophenone;

2,6-dichloro-3',4'-dimethoxy-2'-(2-methoxy-ethoxy)-6'-methylbenzophenone;

2,6-dichloro-3',4'-dimethoxy-6'-methyl-2'-(3-methylbutoxy)benzophenone;

2,6-dichloro-3',4'-dimethoxy-6'-methyl-2'-(prop-2-ynyloxy)benzophenone;

2,6-dichloro-3',4,-dimethoxy-6'-methyl-2'-pentyloxybenzophenone;

2,6-dichloro-3',4'-dimethoxy-6'-methyl-2'-propoxybenzophenone;

2,6-dichloro-4',5'-dimethoxy-2'-methylbenzophenone;

2,6-dichloro-4'-methoxy-2'-methyl-5'-(3-methylbutoxy)benzophenone;

2,6-dichloro-4'-methoxy-2'-methyl-5'-(prop-2-ynyloxy)benzophenone;

2,6-dichloro-4'-methoxy-2'-methyl-5'-(octyloxy)benzophenone;

2,6-dichloro-4'-methoxy-2'-methyl-5'-(pentyloxy)benzophenone;

2,6-dichloro-4'-methoxy-2'-methyl-5'-propoxybenzophenone;

2,6-dichloro-4'-methoxy-2'-methyl-5'-trimethylsilanylmethoxybenzophenone;

2,6-dichloro-5'-(1-ethyl-propoxy)-4'-methoxy-2'-methylbenzophenone;

2,6-dichloro-5'-difluoromethoxy-4'-methoxy-2'-methylbenzophenone;

2,6-dichloro-5'-ethoxy-4'-methoxy-2'-methylbenzophenone;

2,6-dichloro-5'-heptyloxy-4'-methoxy-2'-methylbenzophenone;

2,6-dichloro-5'-hexyloxy-4'-methoxy-2'-methylbenzophenone;

2,6-dichloro-5'-isobutoxy-4'-methoxy-2'-methylbenzophenone;

2,6-dichloro-5'-isopropoxy-4'-methoxy-2'-methylbenzophenone;

5'-butoxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone;

5'-cyclohexylmethoxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone;

5'-cyclohexyloxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone;

5'-cyclopentyloxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone;

5'-cyclopropylmethoxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone; or

5'-decyloxy-2,6-dichloro-4'-methoxy-2'-methyl-benzophenone.

The present invention also provides benzophenone compounds of formula Ia##STR4## wherein R¹ represents a halogen atom, an optionally substitutedalkyl group or a cyano group; m is an integer of 2, 3 or 4; R²independently represents a halogen atom, an optionally substituted alkylor alkoxy group or when R¹ and R² are on adjacent carbon atoms, R¹ R²together represent --CH═CH--CH═CH-- or an optionally substitutedalkylene or oxyalkyleneoxy group; R³ represents a hydrogen or halogenatom, an optionally substituted alkyl, alkoxy, alkenyl, alkylthio,alkylsulphinyl, alkylsulphonyl, cyano, carboxy, hydroxy, nitro, or anoptionally substituted amino group; R⁴ represents an optionallysubstituted alkyl or acyl group; R⁵ represents a halogen atom, anoptionally substituted alkoxy, alkenyloxy, alkynyloxy, alkylthio,cycloalkyl, cycloalkyloxy, trialkylsilyloxy, --ONa, --OK, --OC(O)R⁷,--OCHR⁸ C(O)R⁷, --OC(O)NR⁸ R⁹, --OS(O)₂ R⁸, --OS(O)₂ NR⁸ R⁹, --OP (X¹)(OR⁸)OR⁹, --OP(X¹)(R⁸)R⁹, --S(O)R⁸ or --S(O)₂ R⁸ group or R⁴ and R⁵ maybe taken together to represent an optionally substituted alkylene oralkyleneoxy chain; n is 0 or an integer of 1 or 2; R⁶ independentlyrepresents an optionally substituted alkoxy group, a hydroxy group or a--OC(O)R¹⁰ group when attached to adjacent carbon atoms, or R⁵ and oneR⁶ may be taken together to represent --CH═CH--CH═CH-- or an optionallysubstituted oxyalkyleneoxy chain; R⁷ represents a hydrogen atom or anoptionally substituted alkyl or alkoxy group; R⁸, R⁹ and R¹⁰independently represent a hydrogen atom or an alkyl group, or R⁸ and R⁹may be taken together to represent an alkylene chain optionallyinterrupted by an oxygen or nitrogen atom; X represents an oxygen atom,a sulphur atom or an NOR group; X¹ represents an oxygen or sulphur atom;Y represents an oxygen or sulphur atom or a sulphonyl or sulphinylgroup; and R represents a hydrogen atom or an optionally substituted,alkyl, aralkyl, aryl or acyl group, with the provisos that when Xrepresents an oxygen or sulphur atom and:

(i) when R¹ represents a halogen atom, then (R²)_(m) must be other thana halogen atom or no more than one alkyl or alkoxy group.

(ii) when R¹ represents an alkyl group, then R² must be other thanalkyl;

(iii) when m is 1, then R² must be other than an alkoxy group;

(iv) when R³ represents an alkenyl group, then R³ cannot be substitutedwith an alkoxy or acyl group;

(v) when R³ represents a haloalkyl group, then R¹ and R² must be otherthan a haloalkyl group; and

(vi) when Y represents an oxygen atom, then R³ and R⁵ must be other thana hydrogen atom and n must be 1 or 2.

The compounds having formula I (including those of formula Ia) may beprepared by a process which comprises reacting a compound of formula II##STR5## with a compound of formula III ##STR6## wherein R¹, R², R³, R⁴,R⁵, R⁶, Y, m and n are as hereinbefore defined and one of Z¹ and Z²represents a hydrogen atom and the other represents the group COCl; orone represents a magnesium halide group MgHal, wherein Hal is a halogen,preferably bromine or iodine, atom, and the other represents COCl or analdehyde or nitrile group, followed in the last two cases by oxidationor hydrolysis, respectively, and optionally followed by furtherderivatization.

The starting materials of formula II and III are known products, and maythemselves be prepared according to established methods or routineadaptations thereof. Substituents R¹ to R⁹ which are not compatible withthe selected reaction conditions may be introduced after formation ofthe benzophenone. They may be generated by known methods such assubsequent derivatization or substitution of a suitable group or bycleaving off a suitable protecting group.

When one of Z¹ and Z² is hydrogen and the other is COCl, the process isa Friedel Crafts reaction and is effected in the presence of a Lewisacid catalyst according to well-established procedures. Suitablecatalysts include AlCl₃, SnCl₄, FeCl₃, ZnCl₂, TiCl₄, SbCl₅ and BF₃,which may be in a molar equivalent amount (based on the acyl chloride).However, it is also possible to use lesser amounts of catalyst atelevated temperatures, suitably under reflux temperatures, preferredcatalysts under these conditions being FeCl₃, I₂, ZnCl₂, iron, copper,strong sulphonic acids such as F₃ CSO₃ H, and acidic ion exchange resinssuch as Amberlyst® 15 and Nafion®. The reaction can be carried out in asolvent inert under the reaction conditions, for example ethylene ormethylene chloride, benzene, decane or solvent mixtures, or in theabsence of solvent, conveniently by employing one of the reactants inexcess.

When the magnesium halide is reacted with a nitrile, i.e. the othergroup Z¹ or Z² represents CN, the immediate reaction product is an imineof formula IV: ##STR7## This intermediate is readily converted to thedesired benzophenone derivatives of formula I wherein X is an oxygenatom by acid hydrolysis, suitably using mineral acids such ashydrochloric or sulphuric.

When magnesium halide is reacted with an aldehyde, i.e. the other groupZ¹ or Z² represents CHO, the immediate reaction product is a tertiaryalcohol of formula V: ##STR8## This formula V intermediate is readilyconverted to the desired benzophenone derivatives of formula I wherein Xis an oxygen atom by oxidation, suitably using Mn(IV), Mn(VII), Ce(IV)or Cr(VI) derivatives, nitric acid or oxygen in the presence of acatalyst.

Certain oxime derivatives of formula I may be prepared by reacting theappropriately substituted nitrile oxide of formula VI with a suitableo-dimethoxybenzene of formula VII in the presence of aluminum chlorideand an inert solvent to form an intermediate and hydrolyzing theintermediate in aqueous acid to give the desired product compounds ofIb. The reaction is shown in flow diagram I. ##STR9##

For compounds of formula Ib the substituents R¹, R², R³, R⁶ and n are asdefined hereinabove for formula I and Ia and m is an integer of 1, 2 or3. The oximes of formula Ib may be O-alkylated or O-acylated usingconventional alkylation and acylation techniques.

The substituents of the benzophenones produced according to theprocesses of the invention may be derivatized further according toestablished methods or routine adaptations thereof, such ashydrogenation, acylation or cleavage of ether bonds.

The formula Ia compounds of the invention are excellent fungicides,especially for the control of phytopathogenic fungi in agriculture orrelated fields. They are useful for the control of powdery mildewdiseases, particularly of Erysiphe graminis, Podosphaera leucotricha orUncinula necator. Due to excellent plant tolerance, the compounds may beused in all cultivation of plants where infection by the controllablefungi is not desired, e.g. small grain cereals, apples, vine. Theabsence of target crop phytotoxicity at fungus control rates is afeature of the present invention.

The present invention also provides a fungicidal composition whichcomprises a compound of formula I or Ia as defined hereinabove and anagriculturally acceptable carrier. Said composition may contain one ormore compounds of the present invention. Preferably, at least onecarrier in a composition according to the invention is a surface-activeagent. For example, the composition may contain at least two carriers,at least one of which is a surface-active agent.

The compounds according to formula I or Ia may be applied as technicalmaterial, however, said compounds are preferably applied as acomposition comprising, besides the formula I or Ia compounds, adjuvantsand auxiliaries which are known for formulation purposes and aremanufactured into e.g. emulsion concentrates, solutions which may besprayed directly or diluted, diluted emulsions, wettable powders,soluble powders, dusts, granulates, microencapsulates bywell-established procedures. The form of application such as spraying,atomizing, dispersing, pouring may be chosen like the compositionsaccording to the desired objectives and the given circumstances.

It is contemplated, compounds of formula I or Ia may be formulated orapplied, either alone or in combination, with one or more pesticides orplant growth regulants. Pesticides used in combination may beherbicides, insecticides or other fungicides or a combination thereof.When the formula I or Ia compounds are applied in combination withanother pesticide or pesticides, they may be applied simultaneously orsequentially. Among the available fungicides which may be used incombination with formula I compounds are 4,6-dinitro-o-cresol,benalaxyl, benomyl, captafol, captan, carbendazim, chlorothalonil,copper, cymoxanil, dichlofluanid, dichlone, difenoconazole,dimethomorph, diniconzole, dinocap, dithianon, fenpiclonil,fenpropiomorph, hymaxazol, imazalil, iprodione, isoprothiolane,kasugamycin, mancozeb, mepronil, mercuric oxide, oxadixyl, oxolinicacid, penconazole, propineb, pyrifenox, thiabendazole, thiram,tolclofos-methyl, triadimefon, triflumizole, triforine validamycin A,vinclozolin, zineb, ziram, and the like.

The fungicidal compositions of the invention may be prepared bywell-established procedures, e.g. intensive mixing and/or grinding ofthe active ingredients with other substances, such as fillers, solvents,solid carriers, and optionally surface-active compounds (tensides).

Solvents may be aromatic. hydrocarbons, preferably the fractions C₈ toC₁₂, e.g. xylenes or xylene mixtures, substituted naphthalenes, phthalicacid esters, such as dibutyl or dioctyl phthalate, aliphatichydrocarbons, e.g. cyclohexane or paraffins, alcohols and glycols aswell as their ethers and esters, e.g. ethanol, ethyleneglycol mono- anddimethyl ether, ketones such as cyclohexanone, strongly polar solventssuch as N-methyl 2-pyrrolidone, dimethyl sulphoxide, alkyl formamides,epoxidized vegetable oils, e.g. epoxidized coconut or soybean oil,water.

Solid carriers, which may be used for dusts or dispersible powders, maybe mineral fillers, such as calcite, talc, kaolin, montmorillonite,attapulgite., The physical properties may be improved by addition ofhighly dispersed silica gel or highly dispersed polymers.

Carriers for granulates may be porous material, e.g. pumice, brokenbrick, sepiolite, bentonite, non-sorptive carriers may be calcite orsand. Additionally, a multitude of pre-granulated inorganic or organicmaterials may be used, such as dolomite or crushed plant residues.

Suitable surface-active substances may be non-ionogenic, anionic orcationic tensides with good dispersing, emulgating and wettingproperties depending on the nature of the benzophenone compound to beformulated. Tensides may also mean mixtures of tensides.

Suitable tensides may be so-called water-soluble soaps as well aswater-soluble synthetic surface-active compounds. Soaps usually arealkali, earth alkali or optionally substituted ammonium salts of higherfatty acids (C₁₀ -C₂₀), e.g. the sodium or potassium salts of oleic orstearic acid or of mixtures of natural fatty acids which are prepared,for example, from coconut or tallow oil. Furthermore, methyl-taurinesalts of fatty acids may be used. However, so-called synthetic tensidesare preferably used, especially fatty sulphonates, fatty sulphates,sulphonated benzimidazole derivatives or alkyl aryl sulphonates. Thefatty sulphates or fatty sulphonates are normally used as alkali, earthalkali or optionally substituted ammonium salts and have an alkyl moietyof 8 to 22 carbon atoms, whereby alkyl also means the alkyl moiety ofacyl residues, such as the sodium or calcium salt of lignin sulphonicacid, of sulphuric acid dodecylate or of a mixture of fatty alcoholsprepared from natural fatty acids. This also includes the salts ofsulphuric acid esters, sulphonic acids and adducts of fatty alcohols andethylene oxide. The sulphonated benzimidazole derivatives preferablycontain 2 sulphonic acid residues and a fatty acid residue with 8 to 22carbon atoms. Alkyl aryl sulphonates are, for example, the sodium,calcium or triethyl ammonium salts of dodecyl benzene sulphonic acid,dibutyl naphthalene sulphonic acid or of a condensate of naphthalenesulphonic acid and formaldehyde. Furthermore, phosphates, such as thesalts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethyleneoxide adduct or phospholipids, may be used.

Non-ionic tensides are preferably polyglycolether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or non-saturated fattyacids and alkylphenols, which have 3 to 10 glycol ether groups and 8 to20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18carbon atoms in the alkyl residue of the alkyl phenols. Other suitablenon-ionic tensides are the water-soluble, 20 to 250 ethylene glycolether groups containing polyadducts of ethylene oxide and polypropyleneglycol, ethylene diamino polypropylene glycol and alkyl polypropyleneglycol with 1 to 10 carbon atoms in the alkyl moiety, the substancesnormally contain 1 to 5 ethylene glycol units per propylene glycol unit.Examples of non-ionic tensides are nonylphenol polyethoxy ethanols,castor oil polyglycol ether, polyadducts of ethylene oxide andpolypropylene, tributyl phenoxy polyethoxy ethanol, polyethylene glycol,octyl phenoxy polyethoxy ethanol. Furthermore, fatty acid esters ofpolyoxy ethylene sorbitan, such as polyoxy ethylene sorbitan trioleatemay be used.

Cationic tensides preferably are quaternary ammonium salts, which haveat least one alkyl residue with 8 to 22 carbon atoms and, furthermore,low, optionally-halogenated alkyl, benzyl or hydroxyalkyl residues. Thesalts are preferably halides, methyl sulphates or alkyl sulphates, e.g.stearyl trimethyl ammonium chloride or benzyl bis(2-chloroethyl) ethylammonium bromide.

The tensides generally used for compositions of the invention aredisclosed in publications such as:

"McCutheon's Detergents and Emulsifiers Annual", MC Publishing Corp.,Ridgewood, N.J., USA 1981;

H. Stache, "Tensid-Taschenbuch", 2nd ed., C. Hanser, Munich, Vienna,1981;

M. and J. Ash, "Encyclopedia of Surfactants", vol. I-III, ChemicalPublishing Co., New York, N.Y., USA 1980-1981.

The pesticidal compositions of the invention may comprise 0.1% to 95%,preferably 0.1% to 80% of at least one compound of formula I or Ia, 1%to 99.9% of a solid or liquid adjuvant and 0% to 25%, preferably 0.1% to25%, of a tenside.

Exemplary of the compositions of the invention are:

Emulsion Concentrates:

Active ingredient: 1% to 20%, preferably 5% to 10%

Surface-active substance: 5% to 30%, preferably 10% to 20%

Liquid carrier: 50% to 94%, preferably 70% to 85%

Suspension-Concentrates:

Active ingredient: 5% to 75%, preferably 10% to 50%

Water: 94% to 24%, preferably 88% to 30%

Surface-active substance: 1% to 40%, preferably 2% to 30%

Wettable Powder:

Active ingredient: 0.5% to 90%, preferably 1% to 80%

Surface-active substance: 0.5% to 20%, preferably 1% to 15%

Solid carrier: 5% to 95%, preferably 15% to 90%

Dusts:

Active ingredient: 0.1% to 10%, preferably 0.1% to 1%

Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

Granulates:

Active ingredient: 0.5% to 30%, preferably 3% to 15%

Solid carrier: 99.5% to 70%, preferably 97% to 85%

As commodity the inventive fungicidal compositions may preferably be ina concentrated form whereas the end-user generally employs dilutedcompositions. Said compositions may be diluted to a concentration of0.001% of active ingredient (a.i.). The doses usually are in the rangefrom 0.01 to 10 kg a.i./ha.

Said compositions may also comprise other auxiliaries such asstabilizers, defoamer, viscosity controlling agents, thickeners,adhesives, fertilisers or other active ingredients to obtain specialeffects.

For a more clear understanding of the invention, the following specificexamples are set forth below. These examples are merely illustrationsand are not to be understood as limiting the scope and underlyingprinciples of the invention in any way. Indeed, various modifications ofthe invention in addition to those shown and described herein willbecome apparent to those skilled in the art from the following examplesand foregoing description. Such modifications are also intended to fallwithin the scope of the appended claims. The terms HNMR, CIMS and IR asused in the examples hereinbelow designate proton nuclear magneticresonance, mass spectrum and infrared, respectively.

EXAMPLE 1

2,6-Dichloro-4',5'-dimethoxy-2'-methylbenzophenone (Compound 1)

(R¹ =Cl, R² =6-Cl, R³ =CH₃, R⁴ =CH₃, R⁵ =OCH₃, X=O, Y=O, m=1, n=0)

A mixture of 4-methyl-veratrol (76.1 g; 500 mmol), 2,6-dichlorobenzoylchloride (120.4 g; 575 mmol) and iron(III)chloride (0.5 g) is heatedwith stirring. The reaction starts at 90° C. under formation of hydrogenchloride, the main reaction is complete within 10 min at 95° C.Subsequently, the reaction mixture is stirred for another 30 min at 100°C. and then cooled to 65° C. Upon addition of methanol (350 ml) Compound1 begins to crystallize. A water/methanol mixture (1:1 v/v; 300 ml) isthen slowly added at 40° C. and the mixture is cooled to roomtemperature with stirring for 30 min. The solid material is collected byvacuum filtration, three times washed with methanol/water (3:1 v/v; 100ml each) and dried yielding colorless crystals, 148.6 g, (91.4% y) mp101.5° C.

EXAMPLE 2

Derivatization of benzophenones

A) 2,6-Dichloro-4',5'-dimethoxy-2'-nitro-benzophenone (Compound 2)

R¹ =Cl, R² =6-Cl, R³ =NO₂, R⁴ =CH₃, R⁵ =OCH₃, X=O, Y=O, m=1 n=0)

A portion of 2,6-dichloro-3',4'-dimethoxybenzophenone (6.22 g, 20 mmol),prepared analogously to Example 1, is added within 15 min into nitricacid (65%; 40 ml) which is heated to 40° C. The clear solution isstirred for 10 min at 40° C., then 1 h at room temperature. The reactionmixture is then poured into water whereupon a slowly solidifying oilforms. This material is dissolved in a small amount of N,N-dimethylformamide under warming, then methanol is added and the mixture ischilled and filtered giving Compound 2 as yellow crystals, 5.57 g, (78%y) with mp 143° C.

B) 2'-Amino-2,6-dichloro-4',5'-dimethoxybenzophenone (Compound 3)

R¹ =Cl , R² =6-Cl, R³ =NH₂, R⁴ =CH₃, R⁵ =OCH₃, X=O, Y=O, m=1, n=0)

A portion of 2,6-dichloro-3',4'-dimethoxy-2'-nitrobenzophenone (Compound2; 3.56 g, 10 mmol) is added to a mixture of water (50 ml), glacialacetic acid (1 ml) and powdered iron (3.30 g, 60 mmol) within 15 min at70° C. The reaction mixture is stirred at 95° C. for another 3 h. Aftercooling, toluene (50 ml) is added and the solid material removed byvacuum filtration. The filter cake is washed with toluene. The filtrateand washings are combined and washed with water, dried and then appliedonto a flash chromatography column (silica gel, 50 g). The column isconsecutively eluted with toluene, and toluene containing 1%, 2%, 5% and10% of acetone (250 ml each). The fraction eluted by 10% acetone isconcentrated in vacuo to a final volume of 10 ml whereby Compound 3crystallizes yielding yellow crystals, 1.61 g, (49% y) mp 181° C.

C) 2,6-Dichloro-4',5'-dimethoxy-2'-formylamino-benzophenone (Compound 4)

(R¹ =Cl, R² =6-Cl, R³ =NHCHO, R⁴ =CH₃, R⁵ =OCH₃, X=O, Y=O, m=1, n=0)

A mixture of 2'-amino-2,6-dichloro-4',5'-dimethoxybenzophenone (Compound3; 0.82 g, 2.5 mmol) and formic acid (30 ml) is heated at refluxtemperature for 24 h, and evaporated in vacuo. The residue is dissolvedin a small amount of toluene, Compound 4 crystallizes upon addition ofcyclohexane giving colorless crystals, 0.64 g, (72% y) with mp 152° C.

D) 2,6-Dichloro-5'-hydroxy-4'-methoxy-2'-methylbenzophenone (Compound 5)

(R¹ =Cl, R² =6-Cl, R³ =CH₃, R⁴ =CH₃, R⁵ =OH, X=O, Y=O, m=1, n=0)

A mixture of 2,6-dichloro-4',5'-dimethoxy-2'-methylbenzophenone(Compound 1; 2.5 g, 7.7 mmol), hydrogen bromide/acetic acid (33%, 10 ml)and glacial acetic acid (10 ml) is stirred for 1.5 h at 75° C., pouredinto water (100 ml) and twice extracted with dichloromethane (50 mleach). The extracts are combined, dried, and concentrated in vacuo. Theresulting oil is applied onto the top of a flash chromatography column(silica gel, 30 g). Elution is carried out with toluene andtoluene/acetone, 9:1 (500 ml each). The fractions containing thematerial with an R_(f) =0.54 (silica gel; toluene/acetone, 9:1) arecombined and the solvent is evaporated in vacuo until a final volume of20 ml is reached. The solution is then extracted three times withaqueous sodium hydroxide (2N; 30 ml each). The aqueous layer isacidified with hydrochloric acid (6M) and the precipitate is collectedby vacuum filtration and dried to give Compound 5 as colorless crystals,1.1 g, (45.9% y) mp 152° C.

E) 2,6-Dichloro-4'-methoxy-2'-methyl-5'-n-propoxy-benzo-phenone(Compound 6)

(R¹ =Cl, R² =6-Cl, R³ =CH₃, R⁴ =CH₃, R⁵ =O-n-C₃ H₇, X=O, Y=O, m=1, n=0)

A mixture of 2,6-dichloro-5'-hydroxy-4'-methoxy-2'-methylbenzophenone(Compound 5; 1.0 g, 3.2 mmol), n-propyl bromide (0.5 g, 4 mmol),potassium carbonate (2.8 g, 20 mmol) and ethanol (10 ml) is stirred for6 h at 80° C., filtered and the filtrate is evaporated in vacuo. Theresidue is applied onto a flash chromatography column (silica gel, 30g). Elution with toluene (750 ml) yields Compound 6 as a brown oil, 800mg, (70.7% y) which slowly crystallizes (mp 73°-75° C.).

F) 2,6-Dichloro-4',5'-dimethoxy-2'-methyl-benzophenthione (Compound 7)

(R¹ =Cl, R² =6-Cl, R³ =CH₃, R⁴ =O--CH₃, R⁵ =O--CH₃, X=S, Y=O, m=1, n=0)

A mixture of 2,6-dichloro-4',5'-dimethoxy-2'-methylbenzophenone(Compound 1; 3.25 g, 10.0 mmol), phosphorus pentasulphide (2.22 g, 10.0mmol) and toluene (50 ml) is stirred at 110° C. for 5 h, treated withp-dioxane, stirred at 100° C. for a further 24 h. The supernatant isdecanted from black, tarry reaction products, silica gel (15 g) is addedand the solvent is evaporated in vacuo. A flash chromatography column ispacked with silica gel (100 g) and the charged silica gel is layered ontop of it. The column is subsequently eluted with petrol ether/acetone(500 ml, 98:2, v/v) and petrol ether/acetone (750 ml, 95:5, v/v)yielding Compound 7 as a dark green oil 40 mg, (1.2% y), which slowlysolidifies. When the oil is triturated with cyclohexane three times, itgives a solid, mp 142° C.

EXAMPLE 3

Using essentially the same procedures described hereinabove for Examples1 and 2 and employing standard derivatization techniques whereappropriate, the following compounds are prepared and shown in Table I.

    TABLE I                                                                          -                                                                              ##STR10##                                                                                                                                              C     omp.                                                                            No. R.sup.1 R.sup.2 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 Y Mp              °C.                                                                       8 Cl 6-Cl H CH.sub.3 CH.sub.3 OC.sub.2 H.sub.5 H O                            87                   9 Cl 6-Cl H CH.sub.3 C.sub.2 H.sub.5 OCH.sub.3 H O       106                                                                             10 Cl 6-Cl H CH.sub.3 CH.sub.3 Cl H O 168                                      11 Cl 6-Cl 3-NO.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 H O oil                      12 Br H H CH.sub.3 CH.sub.3 OCH.sub.3 H O 69-71                                13 Cl 6-Cl H CH.sub.3 CH.sub.3 OC(O)C.sub.2 H.sub.5 H O 142-145                         14 Cl 6-Cl H CH.sub.3 CH.sub.3 H H O                                  89                         15 I H H CH.sub.3 CH.sub.3 OCH.sub.3 H O           66-68                                                                            16 Cl 6-CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O                            56                   17 Cl 6-CH.sub.3 H F CH.sub.3 OCH.sub.3 H O  95           18 (CHCH).sub.2 6-Cl CH.sub.3 CH.sub.3 OCH.sub.3 H O                          19 I 3-I 5-I CH.sub.3 CH.sub.3 OCH.sub.3 H O oil                                20 Br 5-Br H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil                               21 Cl 4-NO.sub.2 H CH.sub.3 CH.sub.3 OCH.sub.3 H O 126-128                     22 Cl 6-Cl H CH.sub.3 CH.sub.3 SCH.sub.3 H S 105                               23 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2-OCH.sub.3 O                         92                24 Cl 6-Cl H CH.sub.3  CH.sub.2                              O H O 142                                                                      25 Cl 6-Cl H CH.sub.3 CH.sub.3 I H S              26 Br 5-OCH.sub.3 H         CH.sub.3 CH.sub.3 OCH.sub.3 I O oil                                             27 Cl 5-Br H CH.sub.3 CH.sub.3 OCH.sub.3 I O 94-96                             28 Cl 6-Cl H CH.sub.3 CH.sub.3 OC(O)CH(CH.sub.3).sub.2 I O 132-135                   29 Cl 5-Cl 6-OCH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 I O oil               30 Cl 6-Cl H CF.sub.3 CH.sub.3 Cl I O                             31 Cl       6-Cl H CH.sub.3 CH.sub.3 OCHF.sub.2 I O 126-128                                  32 CF.sub.3 5-CF.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 I O  98-101              33 Cl 6-Cl H CH.sub.3 CH.sub.3 H 3-OCH.sub.3 O 100-125             34         Cl 6-Cl H CH.sub.3 CH.sub.3 OC(O)C(CH.sub.3).sub.3 H O 167                      35 Cl 6-Cl H CH.sub.3 H OH H O 201-203                                         36 Cl 6-Cl H SCH.sub.3 CH.sub.3 OCH.sub.3 H O 185                              37 Cl 6-Cl H S(O.sub.2)CH.sub.3 CH.sub.3 OCH.sub.3 H O 163                     38 Cl 6-Cl H CH.sub.3 CH.sub.3 CH.sub.3 3-CH.sub.3 O                           78                  39 Cl 6-Cl H S(O)CH.sub.3 CH.sub.3 OCH.sub.3 H O          178                                                                              40 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2                                      CHCH.sub.2 H O oil              41 Cl 3-Cl 5-Cl CH.sub.3 CH.sub.3             OCH.sub.3 H O                                                                   99-101                                                      42 Cl 6-Cl        H CH.sub.3 CH.sub.3 (CH.sub.2).sub.2                                            O H O oil                             43 Cl 6-Cl H CH.sub.3 CHF.sub.2         OCHF.sub.2 H O 65-68                                                             44 CF.sub.3 6-CF.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O 105-107              45 Cl 6-Cl H CHCH.sub.2 CH.sub.3 OCH.sub.3 H O                     46 I       6-F H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil                                        47 Cl 3-Cl H CH.sub.3 CH.sub.3 OC.sub.2 H.sub.5 H O                           97                  48 Cl 6-Cl H CH.sub.3 C.sub.2 H.sub.5 OC.sub.2            H.sub.5 H O                                                                     77                                                            49 Cl           6-Cl H CHCHCN CH.sub.3 OCH.sub.3 H O                                             50 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 3-Br O                               86                      51 Cl 4-Cl 5-Cl CH.sub.3 CH.sub.3 OCH.sub.3 H O       160                                                                              52 Cl 6-Cl H CH.sub.3 CH.sub.3 C.sub.4 H.sub.9                                -t H O 124                53 Cl 6-Cl H CH.sub.3 CH.sub.3 OC.sub.4             H.sub.9 -n H O                                                                  51                                                         54 Cl 6-Cl H       CH.sub.3 CH.sub.3 OC.sub.4 H.sub.9                                              -i H O oil                              55 Cl 6-Cl H CH.sub.3 CH.sub.3        H H S                                                                            56 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 C.sub.6 H.sub.5 H O 119-121             57 Cl 6-Cl H CH.sub.3 CH.sub.3 OC.sub.5 H.sub.11 -n H O 46-48                       58 Cl 6-Cl H CH.sub.3 CH.sub.3 OC.sub.3 H.sub.7 -i H O oil             59 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2-OH O 161                 60        Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 C(O)OC.sub.2 H.sub.5 H O 105-108          61 Cl 6-Cl H CH.sub.3 CH.sub.3 H 2-OCH.sub.3 O 135                            62 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2-OC.sub.2 H.sub.5 O  72               63 Cl 6-Cl H CH.sub.3 CH.sub.3 Cl H S                             64 Cl       4-Cl 6-Cl CH.sub.3 CH.sub.3 OCH.sub.3 H O 108-109                               65 Cl 6-Cl H CH.sub.3 CH.sub.3 Br H S                                          66 F 6-F H CH.sub.3 CH.sub.3 OCH.sub.3 H O 75-77                               67 Cl H H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil                                  68 Cl 4-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil                               69 Cl 6-Cl H CH.sub.3 CH.sub.3 CH.sub.3 H O 135-138                            70 Cl 6-Cl H CF.sub.3 CH.sub.3 Br H O                                          71 Cl 5-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 H O 100-102                           72 Cl 6-Cl H C.sub.2                                                           H.sub.5 CH.sub.3 OCH.sub.3 H O oil                   73 Cl 3-Cl H             CH.sub.3 CH.sub.3 OCH.sub.3 H O oil                                             74 Cl 6-Cl H CN CH.sub.3 OCH.sub.3 H O 120                                     75 F 6-CF.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil                           76 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2                                      CN H O 127                      77 Cl 6-F H CH.sub.3 CH.sub.3 OCH.sub.3       H O 72-73                                                                       78 Cl 6-Cl H I CH.sub.3 OCH.sub.3 H O 101                                      79 Cl 6-Cl H C.sub.3 H.sub.7 -n CH.sub.3 OCH.sub.3 H O                         72                80 Cl 6-Cl H CH.sub.3 CH.sub.3 OC(O)CH.sub.3 H O            156-159                                                                         81 Cl 6-Cl H Br CH.sub.3 OCH.sub.3 H O 124                                     82 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 CCH H O                               87                      83 Cl 6-Cl H H CH.sub.3 H 3-OCH.sub.3 O 127            84 Cl 6-Cl H CH.sub.3 H H 3,6-di-CH.sub.3 O 122                      85       Cl 6-Cl H CH.sub.3 CH.sub.3 H 3,6-di-CH.sub.3 O 111                              86 Cl 6-Cl H CF.sub.3 C(O)-2,6-Cl.sub.2 C.sub.6 H.sub.3 H H O 186                   87 CH.sub.3 6-CH.sub.3 H H CH.sub.3 H 3-OCH.sub.3 O                      84                                                                             88 Cl 6-Cl H H CH.sub.3 H 3-Br O 129                       89 Cl 6-Cl H       H CH.sub.3 Br 3-OCH.sub.3 O 140                                                 90 Cl 6-Cl H OCH.sub.3 CH.sub.3 OCH.sub.3 H O 124                              91 Cl 6-Cl H CH.sub.3 CH.sub.3 OC(O)H H O 156                                   92 OCH.sub.3 6-OCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O 113                93 Cl 6-Cl H COOH CH.sub.3 OCH.sub.3 H O 174                     94 Cl        6-Cl H CH.sub.3 CH.sub.3 S(O).sub.2                                             CH.sub.3 H SO.sub.2 233                95 Cl 6-Cl H CH.sub.3 CH.sub.3         SOCH.sub.3 H SO 227                                                              96 Cl 6-Cl H CH.sub.3 CH.sub.3 O.sub.n -C.sub.7 H.sub.15 H O oil                     97 Cl 6-Cl H CH.sub.3 CH.sub.3 O.sub.n -C.sub.8 H.sub.17 H O oil         98 Cl 6-Cl H CH.sub.3 CH.sub.3 O.sub.n -C.sub.10 H.sub.21 H O oil                   99 CH.sub.3 4-CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 H O        74                                                                             100 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 -c-C.sub.3 H.sub.5 H O oil              101 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 -c-C.sub.6 H.sub.11 H O          108                                                                             102 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.2CH(CH.sub.3).sub.2 H O       oil                                                                             103 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 CHC(CH.sub.3).sub.2 H O oil            104 CH.sub.3 6-CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O 90-92                    105 Cl 6-Cl H CH.sub.3 CH.sub.3 Oc-C.sub.5 H.sub.9 H O oil                      106 Cl 6-Cl H CH.sub.3 CH.sub.3 Oc-C.sub.6 H.sub.11 H O oil                  107 Cl 6-Cl H H CH.sub.3  3!-(CHCH).sub.2 - 2! H O 155-157                        108 Cl 6-Cl H CH.sub.3 CH.sub.3 ONa H O glass                          109 Cl 6-Cl H CH.sub.3 CH.sub.3 OSi(CH.sub.3).sub.3 H O oil                    110 Br 6-Br H CH.sub.3 CH.sub.3 OCH.sub.3 H O 102                              111 Cl 6-Cl H CH.sub.3 CH.sub.3 Oh H O                                         98                               112 Cl 6-Cl H OCH.sub.3 CH.sub.3 Br          2-OCH.sub.3 O 183                                                               113 CN H H CH.sub.3 CH.sub.3 OCH.sub.3 H O                                     76                           114 Cl 6-Cl H CH.sub.3 CH.sub.2                   O 2-OCH.sub.3                                                                  98                                                        115 Cl 6-Cl H N     HCH.sub.3 CH.sub.3 OCH.sub.3 H  163                                             116 Cl 6-Cl H OH CH.sub.3 OCH.sub.3 H O                                        80                              117 Cl 6-Cl H CH.sub.3 CH.sub.3               OCH.sub.2Si(CH.sub.3).sub.3 H O oil                                             118 Cl H H CH.sub.3 CH.sub.3 OCH.sub.3 H O 62-64                               119 Cl 3-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2-OCH.sub.3 O oil                    120 Cl 4-Cl 6-Cl CH.sub.3 CH.sub.3 OCH.sub.3 H O 126                           121 F 6-F H CH.sub.3 CH.sub.3 OCH.sub.3 H O                                    84                          122 Cl 5-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 H       O oil                                                                           123 Cl 6-Cl H OCH.sub.3 CH.sub.3 CH.sub.3 6-OCH.sub.3 O 115                    124 I H H CH.sub.3 CH.sub.3 OCH.sub.3 2-OCH.sub.3 O oil                        125 Br H H CH.sub.3 CH.sub.3 OCH.sub.3 H O                                     34                           126 Cl 6-Cl H CH.sub.3 CH.sub.3 On-C.sub.6       H.sub.13 H O oil                                                                127 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2On-C.sub.3 H.sub.7 O  46                128 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2On-C.sub.7 H.sub.15 O          oil                                                                             129 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2On-C.sub.10 H.sub.21 O oil            130 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2-OC(O)CH.sub.3 O 164                    131 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2On-C.sub.5 H.sub.11 O        oil                                                                             132 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2O(CH.sub.2).sub.2CH(CH.sub.3)      .sub.2 O 101                                                                    133 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2OCH.sub.2CHCH.sub.2 O  73              134 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2OCH.sub.2 CCH O 123                    135 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2Oc-C.sub.5 H.sub.9 O         89                                                                              136 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 6OCH.sub.2C.sub.6 H.sub.5 O         80                                                                              137 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2On-C.sub.12 H.sub.25 O oil            138 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2OCH.sub.2 -c-C.sub.6             H.sub.11 O                                                                      88                                                            139 Cl          6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2On-C.sub.6                                  H.sub.13 O oil             140 Cl 6-Cl H CH.sub.3 CH.sub.3 On-C.sub.12        H.sub.25 H O oil                                                                141 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 C(O)N(C.sub.2 H.sub.5).sub.2        H O                                                                             97                                                                            142 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2                                       C(O)NH.sub.2 H O 136            143 Cl 6-Cl H CH.sub.3 CH.sub.3               OCH.sub.3 2O(CH.sub.2).sub.2OCH.sub.3 O                                         84                               144 Cl 6-Cl H CH.sub.3 CH.sub.3              OCH(C.sub.2                                                                     H.sub.5).sub.2 H O oil                                        145 Cl          6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.2OH H O                                87                      146 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.      3OH H O                                                                         86                                                               147 Cl       6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 -p-C.sub.6 H.sub.4CH.sub.3 H O oil              148 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 -p-C.sub.6                        H.sub.4C(CH.sub.3).sub.3 H O 119                                               149 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2OCH.sub.2 C(O)-morpholide O        oil                                                                             150 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.2 OCH.sub.3 H O oil                151 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2C(O)-morpholide H O 163              152 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 -p-C.sub.6 H4OCH.sub.3 H O       oil                                                                             153 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.3 OC.sub.6 H.sub.5 H O        oil                                                                             154 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2O(CH.sub.2).sub.3 -morpholin       yl ×                                                                      HCl O 225                                                      155 Cl         6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2O(CH.sub.2).sub.2N(CH.sub.3).sub.2         ×                                                                         HCl O 103                                                         156         Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2O(CH.sub.2).sub.2N(C.sub.2              H.sub.5).sub.2 ×                                                          HCl O 144                                          157 Cl 6-Cl H              CH.sub.3 CH.sub.3 OC.sub.2 H.sub.5 2-OCH.sub.3 O                                68                      158 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3             2O(CH.sub.2).sub.3 Cl O                                                         87                                               159 Cl 6-Cl H CH.sub.3       CH.sub.3 OCH.sub.3 2O(CH.sub.2).sub.3 -piperidyl × HCl O  70                    160 Cl 6-Cl H CH.sub.3 n-C.sub.7 H.sub.15 OCH.sub.3 H O  51                    161 Cl 6-Cl H CH.sub.3 n-C.sub.3 H.sub.7 OCH.sub.3 H O  80                      162 Cl 6-Cl H CH.sub.3 n-C.sub.4 H.sub.9 OCH.sub.3 H O  89                    163 Cl 6-Cl H CH.sub.3 CH.sub.3 CH(CH.sub.3).sub.2 H O  96                      164 CH.sub.3 3-CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 6-OCH.sub.3       O                                                                              82                                                                            165 CH.sub.3 5-CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 6-OCH.sub.3 O oil          166 Cl 6-Cl H Cl CH.sub.3 OCH.sub.3 H O 114                                   167 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.3CO.sub.2 C.sub.2             H.sub.5 H O oil                                                                 168 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 C.sub.6 H.sub.4CF.sub.3 -p H        O 115-117                                                                       169 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 SiC.sub.2 H.sub.5                    (CH.sub.3).sub.2 H O                                                           85                                                 170 Cl 6-Cl H              CH.sub.3 CH.sub.3 OC(CH.sub.3).sub.3 H O 102                                    171 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2         OCH H O oil                                                                     172 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2)4Br H O oil                         173 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 6-O(CH.sub.2).sub.3 N(C.sub.2       H.sub.5).sub.2 O oil                                                            174 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 6-OCH(CH.sub.3).sub.2 O 108            175 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 6-OCH.sub.2                        CH.sub.2OCH.sub.2 CH.sub.2                                                     OCH.sub.3 O oil                               176 Cl 6-Cl H CH.sub.3          CH.sub.3 OCOC.sub.6 H.sub.3 Cl.sub.2                                            -2,6 6-OCH.sub.3 O 186-189           177 Cl 6-Cl H H CH.sub.3 OCH.sub.3       6-OCH.sub.3 O                                                                   97                                                         178 Cl 6-Cl        H CH.sub.3 CH.sub.3 CH.sub.3 6-OCH.sub.3 O 106                                  179 Cl 6-Cl H OCH.sub.3 CH.sub.3 OCH.sub.3 6-OCH.sub.3 O 121-123                      180 Cl 6-Cl H CH.sub.3 CH.sub.3 NHCOCH.sub.3 H O 155                    181 Cl 6-Cl H CH.sub.3 CH.sub.3 OH 6-OH O 182                                  182 CF.sub.3 H H CH.sub.3 CH.sub.3 OCH.sub.3 6-OCH.sub.3 O oil                 183 CF.sub.3 H H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil                           184 Cl 6-Cl H CH.sub.3 CH.sub.3 OC.sub.4 H.sub.9 -n 6-OC.sub.4 H.sub.9        -n O oil                                                                        185 Cl 6-Cl H CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 H O 110                     186 Cl 6-Cl H CH.sub.3 H NO.sub.2 H O 149                                

EXAMPLE 4

2'-n-Butoxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone (Compound187)

(R¹ =Cl, R² =6-Cl, R³ =CH₃, R⁴ =CH₃, R⁵ =OCH₃, R⁶ =2--O--(CH₂)₃ --CH₃,X=O, Y=O, m=1, n=1)

a) 2,6-Dichloro-3',4'-dimethoxy-2'-hydroxy-6'-methylbenzophenone(Compound 59)

Aluminum chloride (14.67 g, 0.1 mol), 2,6-dichlorobenzoyl chloride(20.95 g, 0.1 mol) and a solution of 3,4,5-trimethoxytoluene (18.22 g,0.1 mol) in dichloromethane (50 ml), are slowly and consecutively addedto dichloromethane stirred at 0° C., stirred for 1 h at ice bathtemperatures and for 16 h at room temperature, and poured into ice. Theorganic layer is separated, washed with dilute hydrochloric acid andwater, dried, and, after addition of silica gel (100 g), concentrated invacuo. A flash chromatography column is packed with silica gel (400 g)and the charged silica gel is layered on top of that. Elution withpetrol ether/ethyl acetate (90/10, 1 l; 80/20, 1 l; 50/50, 1l) yields2,6-dichloro-3'4'-dimethoxy-2'-hydroxy-6'-methylbenzophenone, 10.35 g,(30% y).

b) 2,6-Dichloro-3',4'-dimethoxy-2'-hydroxy-6'-methylbenzophenone,potassium salt (Compound 188)

(R¹ =Cl, R² =6-Cl, R³ =CH₃, R⁴ =CH₃, R⁵ =OCH₃, R⁶ =2-OK, X=O, Y=O, m=1,n=1)

A solution of2,6-dichloro-3',4'-dimethoxy-2'-hydroxy-6'-methyl-benzophenone (10.24 g,30 mmol) is dissolved in ethanolic potassium hydroxide (1.98 g, 30 mmol;85% in ethanol (100 ml)) and stirred at 70° C. for 15 min. The solventis then evaporated in vacuo. The residue is dissolved in hot ethanol (50ml), toluene is added and the solvent is evaporated in vacuo givingCompound 188, 11.7 g.

c) 2'-n-Butoxy-2,6-dichloro-3',4'-dimethoxy-6,-methylbenzophenone(Compound 187)

A mixture of2,6-dichloro-3',4'-dimethoxy-2'-hydroxy-6'-methyl-benzophenone,potassium salt (1.13 g; 3 mmol), 1-bromobutane (0.69 g, 5 mmol) anddimethyl formamide (5 ml) are stirred at 100° C. for 8 h, andconcentrated in vacuo. The residue is dissolved by shaking with atoluene/water mixture, after separation, the organic layer is collectedwashed with water and dried. After addition of silica gel (5 g), thesolvent is evaporated. A flash chromatography column is packed withsilica gel (25 g) and the charged silica gel is layered on top of that.Elution with petrol ether/ethyl acetate (95/5, 500 ml) gives the titlecompound, 0.82 g, (69% y) as colourless crystals, mp. 70° C.

EXAMPLE 5

Using essentially the same procedures described in Examples 1, 2 and 4hereinabove and employing, if required, standard derivativatizationmethods, the following compounds shown in Table II are prepared

                                      TABLE II                                    __________________________________________________________________________     ##STR11##                                                                    Comp.                                                                         No. R.sup.1                                                                          R.sup.2                                                                             m R.sup.3                                                                          YR.sup.4                                                                          R.sup.5   R.sup.6                                                                           n mp °C.                           __________________________________________________________________________    189 CH.sub.3                                                                         2,3,5,6-CH.sub.3                                                                    4 CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3 H   0 103                                     190 CH.sub.3                                                                         CH.sub.3                                                                            5 CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3 H   0   142-144.5                             191 CH.sub.3                                                                         2,3,5,6-CH.sub.3                                                                    4 CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3 5-OCH.sub.3                                                                       1 113                                     192 CH.sub.3                                                                         2,3,5,6-CH.sub.3                                                                    4 CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                   H   0  73                                     193 CH.sub.3                                                                         2,3,5,6-CH.sub.3                                                                    4 CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.2 CH.sub.2 CH.sub.3                                                             H   0  85                                     194 CH.sub.3                                                                         2,3,5,6-CH.sub.3                                                                    4 CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3 5-OH                                                                              1 137                                     __________________________________________________________________________

EXAMPLE 6

2,6-Dichloro-3',4'-dimethoxybenzophenone oxime (Compound 195)

R¹ =Cl; R² =6-Cl; R³ =H; Y=O; R⁴ =CH3; R⁵ =H; R⁶ =4-OCH₃ ; R=H

A stirred dispersion of anhydrous aluminum chloride (2.93 g, 22 mmol) inmethylene chloride at ice-bath temperatures is treated sequentially witha solution of 2,6-dichlorobenzonitrile oxide (3.76 g, 20 mmol) inmethylene chloride and, dropwise, with a solution of veratrole (3.32 g,24 mmol) in methylene chloride, stirred for 0.5 hour, allowed to warm toroom temperature, stirred for 4-5 hours and poured into a mixture of iceand HCl. The resultant phase mixture is separated. The organic phase iswashed with 2M HCl, treated with silica gel and evaporated to dryness invacuo. The residue is placed on top of a column of silica gel and elutedwith mixtures of petroleum ether and ethyl acetate (5%, 10% and 20% petether, respectively) to give the title product as a white solid, 1.25 g(19% y) mp 153° C.

EXAMPLE 7

2,6-Dichloro-4', 5'-dimethoxy-2'-methylbenzophenone O-n-propyloxime(Compound 196)

R¹ =Cl; R² =6-Cl; R³ =CH₃ ; Y=O; R⁴ =CH₃ ; R⁵ OCH₃ ; R⁶ =H; R=CH₂ CH₂CH₃

A stirred solution of 2,6-dichloro-4',5'-dimethoxy-2'-methylbenzophenoneoxime (1.5 g, 4.4 mmol) in anhydrous tetrahydrofuran is treated with a60% dispersion of sodium hydride in mineral oil (0.2 g, 4.8 mmol NaH).After the cessation of hydrogen gas evolution, the reaction mixture istreated with n-propyliodide (0.82 g, 5.3 mmol), allowed to stand at roomtemperature for 12 hours, and diluted with water. The resultant phasemixture is extracted with ethyl acetate. The organic phases are combinedand concentrated in vacuo to give a residue. The residue ischromatographed using silica gel and petroleum ether/ethyl acetate, 8/2,to give the title product as a yellow oil, 0.4 g (23.8% y) identified byNMR (67:23, E/Z isomer ratio).

EXAMPLE 8

2,6-Dichloro4',5'-dimethoxy-2'-methylbenzophenone-O-acetyl-oxime(Compound 197)

R¹ =Cl; R² =6-Cl; R³ =CH₃ ; Y=O; R⁴ =CH₃ ; R⁵ =OCH₃ ; R⁶ =H; R=COCH₃

A stirred solution of 2,6-dichloro-4',5'-dimethoxy 2'-methylbenzophenoneoxime (2.3 g, 6.8 mmol) in anhydrous tetrahydrofuran is treated with a60% dispersion of sodium hydride in mineral oil (0.3 g, 7.5 mmol NaH).After the cessation of hydrogen gas evolution, the reaction mixture istreated with acetylchloride (0.55 g, 7.5 mmol) at room temperature,allowed to exotherm to 30° C., stirred at ambient temperatures for 2hours, concentrated in vacuo, treated with water, and filtered. Thefiltercake is washed with water, dried and recrystallized from methanolto give the title product as white crystals, 1.0 g (38.5% y), mp158°-149° C., identified by NMR (100% E isomer).

EXAMPLE 9

Using essentially the same procedures described for Examples 6-8hereinabove the following compounds are obtained and shown in Table III.

                  TABLE III                                                       ______________________________________                                         ##STR12##                                                                    Compound                                                                      No.      R            R3      R6    mp °C.                             ______________________________________                                        198      H            F       H     oil                                       199      H            H       H     153                                       200      H            CH.sub.3                                                                              H     60-70                                     201      H            CH.sub.3                                                                              6-OCH.sub.3                                                                         219-220                                   202      CH.sub.3     CH.sub.3                                                                              H     112-115                                   203      CH(CH.sub.3).sub.2                                                                         CH.sub.3                                                                              H     117                                       204      CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        CH.sub.3                                                                              H     oil                                       ______________________________________                                    

EXAMPLE 10

    ______________________________________                                        Formulation: Emulsion Concentrate                                             ______________________________________                                        active compound    200 g/l                                                    ethoxylated castor oil                                                                           100 g/l                                                    tetrahydrofurfuryl alcohol                                                                       793 g/l                                                    ______________________________________                                    

EXAMPLE 11

The fungicidal activity of the compositions and compounds of theinvention is investigated by means of the following tests.

a) Activity Against Cereal Powdery Mildew (Erysiphe graminis f.sp.hordei and f.sp. tritici)

This test measures the prophylactic activity of test compositions andtest compounds applied as a foliar spray. Cereal seedlings (barley, cvGolden Promise; wheat, cv Kanzler) are grown to the 1 leaf stage. Theplants are then sprayed with a solution of test compound in water, madeup from a 5,000 ppm stock solution in acetone containing 5,000 ppm ofTRITON®X 155 (a non-ionic polyoxyethylene ether surfactant). Plants aretreated using an automated spray line with atomizing nozzles. The sprayvolume is 20 ml. One to three days after treatment, the seedlings areinoculated with powdery mildew by shaking stock culture plants withsporulating pathogen (barley--Erysiphe graminis f.sp. hordei;wheat--Erysiphe graminis f.sp. tritici) over them. Thereafter, theplants are kept for 3h without air movement in order to allow the sporesto settle on the leaves. The plants are then kept in the greenhouseuntil symptoms occur. Assessment is based on the percentage of diseasedleaf area compared with that on control leaves.

b) Activity Against Apple Powdery Mildew (Podosphaera leucotricha)

This test measures the prophylactic activity of test compositions andtest compounds, applied as a foliar spray. Apple seedlings (cvMorgenduft) are grown to the 6-7 leaf stage and then cut back to 3leaves, taking off the oldest and youngest leaves. The plants aresprayed with a solution (20 ml) of test compound in water, made up froma 5,000 ppm stock solution in acetone containing 5,000 ppm of TRITON®X155. The plants are treated using an automated spray line with atomizingnozzles. One to three days after treatment, the seedlings are inoculatedwith powdery mildew by shaking stock culture plants with sporulatingpathogen over them. Thereafter, the plants are kept for 3 h without airmovement. The plants are then kept in the greenhouse until symptomsoccur. Assessment is based on the percentage of diseased leaf area oftreated plants compared with that of control plants.

c) Activity Against Grapevine Powdery Mildew (Uncinula necator)

This test measures the direct protectant activity of test compositionsand test compounds applied as foliar spray. Cuttings of grapevine (cvMuller-Thurgau) are grown to the 6-8 leaf stage and then cut back to 4equally sized leaves. The plants are sprayed to run-off in a spraycabinet with a solution (20 ml) of test compound in water made up from a5,000 ppm stock solution in acetone containing 5,000 ppm of TRITON®X155. Two days after treatment, the cuttings are inoculated with conidiaof Uncinula necator in a special spore setting tower. The spores areblown from freshly sporulating grape leaves (U. necator stock culture)into the upper hole of the settling tower and are allowed to settle onthe leaves for 5 min. Then the plants are kept in a phytotron at 18° C.night and 22° C. day temperature at an interval of 12 h night and 12 hday. Illumination is accomplished by fluorescent tubes at 11,200 lux.Assessment is carried out after 21 days by visual inspection and basedon the percentage of the diseased leaf area of the three youngest leavescompared with that on control plants. The results of the tests are setout in Table IV below, in which the compounds are identified byreference to the preceding Compound Nos. allocated in Examples 1 to 9above. Absence of a rating indicates that none of the tests describedabove was carried out. A rating 0 indicates disease as untreatedcontrol, a rating 100 indicates no disease.

                  TABLE IV                                                        ______________________________________                                        Erysiphe graminis   Podosphaera                                                                              Uncinula                                               barley    wheat     leucotricha                                                                            necator                                  Comp. No.                                                                             100 ppm   100 ppm   100 ppm  200 ppm                                  ______________________________________                                        *1      100       100       96       84                                       *2      99        100       0        41                                       *3      0         6         0                                                 4       95        100       41                                                5       94        99        41                                                6       99        100                                                         *8      100       100       100      95                                       *9      0         70        95                                                *10     85        100       44       88                                       *11     0         0         0                                                 *12     23        0         0                                                 13      87        100                                                         *14     0         36        0                                                 *15     99        73        0                                                 16      100       94                                                          17      25        5         77                                                18      89        57        73                                                19      19        26        15                                                20      100       100       28                                                21      9         19        15                                                23      100       100       100                                               24      94        100       53                                                26      82        79        33                                                27      90        100       89                                                28      100       98                                                          29      99        93        97                                                31      99        100                                                         32      1         28        8                                                 33      39        98                                                          34      0         0                                                           35      0         22        9                                                 36      49        61                                                          37      70        37                                                          38      42        77                                                          39      28        85                                                          40      100       100                                                         41      49        99                                                          43      23        49                                                          44      89        38        10                                                46      100       100                                                         47      95        100                                                         48      84        90        100                                               50      4         6         94                                                51      51        25                                                          52      0         0                                                           53      100       100                                                         *54     100       100                                                         56      100       100       11                                                *57     99        100                                                         *58     100       100                                                         *59     0         1                                                           60      0         32                                                          62      100       100                                                         *64     95        99        71       63                                       *66     0         0         0                                                 *67     43        0         0                                                 *68     0         0         0                                                 *69     0         28        0                                                 *71     99        32        10                                                *72     55        72        0                                                 *73     99        94        26       33                                       *74     0         0         16                                                *75     61        34        0                                                 76      33        57                                                          *77     41        99        90                                                *78     0         85        0                                                 *79     0         0         0                                                 80      76        100                                                         82      100       100                                                         84      0         0                                                           85      33        28                                                          86      0         17                                                          91      93        100                                                         *93     0         17                                                          *94     0         0                                                           *95     91        0                                                           *96     100       100       100                                               *97     100       100       100                                               *98     100       100       100                                               *99     86        6         29                                                *100    100       100       100                                               *101    100       100       87                                                *102    100       100       100                                               *103    100       100       10                                                *104    100       14        27                                                *105    100       100       100                                               *106    100       100                                                         *107    0         21                                                          *108    100       100                                                         *109    100       100                                                         *110    100       100                                                         *111    95        100                                                         *112    0         19                                                          *113    0         28                                                          *114    0         17                                                          *115    100       60                                                          *116    100       64                                                          *117    100       100       6                                                 *118    99        13        66                                                *119    100       89        98                                                *120    100       89        46                                                *121    100       100       37                                                *122    100       100       28                                                *123    0         44        9                                                 *124    100       100       89                                                *125    100       28        8                                                 *126    100       100       100                                               *127    100       100       100                                               *128    100       100       100                                               *129    100       100       100                                               *130    0         78        0                                                 *131    100       100       100                                               *132    100       100       100                                               *133    100       100       100                                               *134    100       100       100                                               *135    100       100       100                                               *136    100       100       100                                               *137    100       100       97                                                *138    100       100       100                                               *139    100       100       100                                               *140    100       100       100                                               *141    97        100       0                                                 *142    97        100       53                                                *143    100       100       100                                               *144    100       100       100                                               *145    84        97        80                                                *146    65        91                                                          *147    100       100                                                         *148    100       100                                                         *149    39        66                                                          *161    48        77        100                                               *162    23        4         100                                               *163    97        90        7                                                 166     100       100       --                                                167     100       97        20                                                168     100       100       2                                                 169     100       100       0                                                 170     100       100       100                                               171     97        100       0                                                 172     100       97        100                                               173     26        53        0                                                 174     100       100       98                                                175     100       100       100                                               176     0         0         8                                                 177     52        0         0                                                 178     100       100       100                                               180     95        19        --                                                181     5         0         6                                                 182     100       93        0                                                 183     100       74        0                                                 184     100       100       100                                               185     0         0         0                                                 186     0         100       100                                               189     100       100       100                                               190     98        8         68                                                191     100       100       99                                                196     0         82        87                                                197     71        78        1                                                 199     0         0         --                                                200     100       100       41                                                201     98        0         --                                                202     0         92        92                                                ______________________________________                                         *indicates the infection with Erysiphe graminis and Podosphaera               leucotricha was carried out 72 h after treatment                         

What is claimed is:
 1. A compound of formula Ia ##STR13## wherein R¹represents halo; m is the integer 1;R² represents chloro; R³ representsan alkyl or alkenyl group; R⁴ represents an alkyl group; R⁵ representsan alkoxy group; R⁶ represents an alkoxy group; n is the integer 1; andX and Y each represents Oxygen.
 2. A compound according to claim 1wherein R¹ is chloro; R³, R⁴, R⁵ and R⁶ each represent a C₁₋₄ alkyl. 3.A compound according to claim 2,2'-butoxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone.